Note: Descriptions are shown in the official language in which they were submitted.
99
The invention concerns a process for the manufacture
of flexible polyurethane foams in which there is used as
organic polyisocyanate a urethane-modified mixture of di- -
phenylmethane diisocyanates and polyphenyl polymethylene
polyisocyanates with a content of 55 to 85 percent by weight
of diphenylmethane diisocyanate, an NCO content of 15 to 30
percent by weight, and a viscosity of 100 to 2000 centipoises
at 20C.
The manufacture of flexible polyurethane foams is
known. Toluene diisocyanates or the commercially available
mixtures of 2,4- and 2,6-toluene diisocyanates are usually
used as polyisocyanates. A disadvantage of this is that
toluene diisocyanates, due to their high vapor pressure, are
relatively strongly toxic and therefore, special precautionary
measures must be taken and observed during their processing.
In order to reduce the toxicity hazard and increase
the reactivity, it has been suggested to replace the toluene
diisocyanates by mixtures of toluene diisocyanates and a -~
mixture of homologous polyaryl polyalkylene polyisocyanates
for the manufacture of polyurethane plastics including foams.
Although mixtures of diphenylmethane diisocyanates
and polyphenylene polymethylene polyisocyanates are less
hazardous due to the markedly lower vapor pressure, the use of
these polyisocyanate mixtures as the sole isocyanate for the
manufacture of flexible polyurethane foams has not caught on
in industry. The primary reason for this is the insufficient
mechanical-property lever, particularly, the very low
breaking elongation of such polyurethane foams. This is all
the more surprising, since mixtures of diphenylmethane
diisocyanates and polyphenylene polymethylene polyisocyanates
as polyisocyanate componen-ts for the manufacture of o-ther
polyurethane-foam types, such as rigid foams, rigid integral-
~.~ - 1 - ~ .
,
,. . ..
9s~9
skin foams, and flexible integral-skin foams, have found
wide-spread application.
According to da~ in sritish Patent 874,~30,
flexible polyurethane foams are manufactured by reaction of
polyether polyols having at least two hydroxyl groups and a
polyisocyanate mixture consisting of diarylmethane diisocyanates
containing 5 to 50 percent by weight of a polyisocyanate
having a functionality gxeater than 2 in the presence of water.
Drawbacks of the described process are the poor processability
of the foamable polyurethane mixtures, which tend to collapse
during foaming and the insufficient mechanical properties of
the foams produced.
This invention concerns an improved process for the
manufacture of flexible polyurethane foams by carrying out a
foaming reaction using a reaction mixture comprising organic
polyisocyanates, polyols, catalysts, foaming agents and
optionally, chain extenders, auxiliaries and additives.
In accordance with this invention, this process is
improved in that:
said organic polyisocyanate has a NCO content of
15 to 30 percent by weight and a viscosity of 100 to 2000
centipoises at 20C;
said organic polyisocyanate is a mixture of diphenyl-
methane diisocyanates and polyphenylene polymethylene poly-
isocyanates containing 55 to 85 percent by weight of di-
phenylmethane diisocyanate based on the total weight of the
polyisocyanate mixture, and
said organic polyisocyanate mixture has been reacted
with a hydroxyl compound having 2 to 3 Zerewitinoff active
hydrogen atoms and a molecular weight of 60 to 1000 in an
equivalency ratio of NCO group to active hydrogen atom of
said hydroxyl compound of 2:1 to 60:1 prior to the reaction
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S99
with other said polyols.
The purpose oE this invention was to manufacture,
without problems, flexible polyurethane foams having good
mechanical properties based on non-toxic polyisocyanates or at
least those of low toxicity.
The problem was solved by a process for the manu-
faeture of flexible polyurethane foams from organic poly-
isocyanates, polyols, eatalysts, foaming agents, and possibly
ehain extenders as we11 as auxiliaries and additives, whieh is
10 eharaeterized by the faet that there are used as organie
polyisocyanates urethane-modified aromatic polyisocyanates
with NCO contents of 15 to 30 percent by weight and a
viscosity of 100 to 2000 centipoises at 20C, which are
obtained by reaction of a mixture of diphenylmethane di-
isocyanates and polyphenylene polymethylene polyisocyanates
eontaining 55 to 85 percent by weight of diphenylmethane
diisoeyanate and a hydroxyl compound having 2 to 4 Zerewitinoff
, ~ ~
.`Y.r: - 3
' ''
1~9~99
active hydrogen atoms and a molecular weight of 60 to 1500
in an equivalency ratio of NCO group to active hydrogen atoms
of the hydroxyl compound of 2:1 to 60:1.
Surprisingly, it was determined that by the selection
of thé urethane-modified polyisocyanate mixture to be used
in accordance with this invention, in combination with the
commonly used polyols and as blo~ing agents, water or mixtures
of water and low-boiling, possibly halogenated hydrocarbons
or dimethyl ether, flexible polyurethane foams having exc~l-
lent mechanical properties are obtained.
An important feature of the process according to
this invention is the use of an aromatic urethane-modified
polyisocyanate mixture as polyisocyanate component, which is
produced by reaction of a mixture of diphenylmethane di-
isocyanates and polyphenylene polymethylene polyisocyanates
containing 55 to 85 percent by weight, pre~erably 60 to 70
percent by weight, of diphenylmethane diisocyanate and
a hydroxyl compound with 2 to 4, preferably 2, Zerewitinoff
active-hydrogen atoms, and a molecular weight of 60 to
20 1500, preferably 120 to 1000, in an equivalency ratio of NCO
group to active-hydrogen of the hydroxyl compound of 2:1
to 60:1, preferably 5:1 to 50~
The mixture of diphenylmethane diisocyanates and
polyphenylene polymethylene polyisocianates with the above-
mentioned content of diphenylmethane diisocyanate can, for `
instance, be ma:nufactured in accordance with the data in
German Published Application No. 24 25 658. The quantity
ratios of the isomeric 4,4'-, 2,4'- and 2,2'-diphenylmethane
diisocyanates to one another in the mixture is not of primar~
importance. According to the inuention, it is primarily
important that the total content of diphenylmethane di-
isocyanate in the mixture corresponds with the above-mentioned
~ 4 ~ `
l~Z9599
concentration conditions. Preferably, however, there are
used those mixtures which contain less than 10 percent by
weight and, in particular, less than 3 percent by weight, of
2,4'-diphenylmethane diisocyanate based on the total weight
of diphenylmethane diisocyanate.
Suitable hydroxyl compounds iwth 2 to 4 Zerewitinoff
active hydrogen atoms and molecular weights of 50 to 1500
include, for instance, alkanolamines such as mono-, di- and
triethanolamine; mono-, di- and tri-isopropanolamine;
nitrogen-atom containing alkoxylation products with molecular
weights of 100 to 1500, preferably of 100 to 500, produced
by alkoxylation of di- to tetrafunctional NH-group-containing
starting molecules, such as possibly N-mono- and N,N'-dialkyl
substituted diamines with 1 to 4 carbon atoms in the alkyl
radical, and 2 to 12, preferably, 2 to 6, carbon atoms in the
alkylene group, such as ethylene diamine, l,4-butanediamine,
and l,6-hexanediamine, and possibly N-mono- and N,N'-
dialkyl-substituted hydrazines with 1 to 4 carbon atoms in the
alkyl radical, such as hydrazine, N,N'-dimethyl hydrazine and
N,N'-dibutyl hydrazine, with alkylene oxides such as ethylene
oxide and propylene oxide or their mixtures, and di- to
tetrafunctional alcohols, such as ethylene glycol, glycerine,
trimethylolpropane and pentaerythritol. Preferabl~ used,
however, are difunctional alcohols such as propylene glycol,
dipropylene glycol, tripropylene glycol, and oligomeric `
polypropylene glycols with molecular weights of up to 1500,
as well as neopentyl glycol.
The aromatic urethane-modified polyisocyanate
mixtures to be used according to this invention have NCO
30 contents of 15 to 30 percent by weight, preferably of 25
to 30 percent by weight, and viscosities of 100 to 2000
centipoises at 20C, preferably 120 to 1500 centipoises at
- 5 -
. ' ' ' ' .
~29599
20C
. For the manufacture o~ flexible polyurethane Eoams
in accordance with the process of this invention, preferably
polyester polyols and, in particular, polyether polyols, are
taken into consideration as polyols. However, other hydroxyl
group-containing polymers having molecular weights of 400 to
7500, such as polycarbonates, in particular, those manu-
factured by the transesterification of diphenyl carbonate with
1,6-hexanediol, polyoxymethylene glycols and polyester amides,
may also be used.
Suitable polyester polyols may, for instance, be
produced from dicarboxylic acids, preferably aliphatic di-
carboxylic acids, havin~ 2 to 12 carbon atoms in the alkylene
radical, and multifunctional alcohols, preferably diols.
These acids include, for instance, aliphatic di-
carboxylic acids such as glutaric acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, undecanedoic acid,
dodecanedioic acid, and preferably, succinic and adipic acids;
cycloaliphatic dicarboxylic acids such as 1,3- and 1,4-cyclo-
?0 hexane dicarboxylic acid; and aromatic dicarboxylic acids such
as phthalic acid and terephthalic acid. Examples of di- and
multifunctional, particularly difunctional, alcohols are: `
ethylene glycol, diethylene glycol, propylene glycol,
dipropylene glycol, 1,3-propanediol, l,lO-decanediol,
glycerine, trimethylolpropane, and preferably, 1,4-butanediol,
and 1,6-hexanediol. If trifunctional alcohols are used for
the manufacture of the polyester polyols, their amount must be
chosen in such a manner that the functionality is a maximum of
` 2.8, preferably 2 to 2.3.
Particularly well proven and, therefore, used on a
preferred basis, are those polyester polyols which are
produced by polycondensation of a dicarboxylic acid mixture
- 6 -
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95~
which, based on the total weight of the named diearboxylie
acids, contains -the following: 20 to 35 percent by weight,
preferably 28 to 33 percent by weight, of suceinic acid; 35 to
50 percent by weight, preferably 40 to 45 percent be weight,
of glutaric acid; and 20 to 32 pereent by weight, preferably
24 to 28 percent by weight, of adipie aeid; and alcohol
mixtures of ethylene glyeol/diethylene glyeol, ethylene
glyeol/trimethylolpropane and diethylene glyeol/trimethylol-
propane. In addition to the named diearboxylie aeids, the
diearboxylic acid mixture may contain up to 5 pereent by
weight, preferably up to 2 to 3 pereent by weight, based on
the total weight, of impurities, whieh consist of primarily
imides of the sueeinie and glutarie aeids. Diearboxylie aeid
mixture of the named type may, for instanee, be obtained as
by-produets during -the manufaeture of adipie aeid by oxidation
of eyelohexanol or eyelohexanone with nitric aeid. The
polyester polyols which have moleeular weights of 500 to 5000,
preferably 1500 to 3000, and funetionalities of 2 to 3O5~
preferably 2 to 2.3, ean be used as such or in the form of
mixtures in accordance with this invention.
However, polyether polyols with moleeular weights of
400 to 7500, preferably 2000 to 5000, and funetionalities of 2
to 3, preferably 2 to 2.3, are partieularly well suited as
polyols. The preferably basieally linear polyether polyols
are manufaetured aeeording to familiar methods from one or
more eyclic ethers, preferably alkylene oxides with 2 to 4
carbon atoms in the alkylene radical, and a starter molecule
whieh contains 2 to 3, preferably 2, active bonded hydrogen
atoms. Suitable cyclic ethers include 1,2- or 2,3-butylene
oxide, styrene oxide, and preferably, ethylene oxide and
1,2-propylene oxide. The alkylene oxides may be used
individually, alternatingly in sequenee, or as mixtures.
~2~59~
Possible starter molecules include: water, dicarboxylic acids
such as succinic-acid, adipic acid, phthalic acid, and tere-
phthalic acid, N,N'-dialkyl substituted diamines with 1 to 4
carbon atoms in the alkyl radical based on, for instance,
ethylene diamine, 1,2- or 1,3-propanediamine, 1,4-butane-
diamine, 1,6-hexanediamine, 4,4'-, 2,4'- and 2,2'-diamino-
diphenylmethane as well as N-alkyldiethanolamine, and pre-
ferably, multifunctional, particularly bifunctional, alcohols
such as ethylene glycol, 1,2- or 1,3-propanediol, diethylene
glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol,
glycerine, and trimethylolpropane. Comparable products
prepared from tetrahydrofuran and oxetane can also be employed.
The polyether polyols can be used as such or in form
of mixtures.
Instead of the polyester polyols or polyether-
polyols, mixtures of polyester polyols and polyether polyols
may also be used. Depending upon the purpose of the flexible
foam to be manufactured, the ratio of the components can vary
within wide limits, for instance, in weight ratios of poly-
20 ester polyol to polyether polyol of 80:20 to 5:95.
It may be advantageous to use chain extenders for
the manufacture of the flexible polyurethane foams in addition
to the above-mentioned polyols. -Particularly, difunctional
compounds with molecular weights of 18 to less than 300, come
into consideration as chain extenders. Preferably there are
used aliphatic diols with 2 to 6 carbon atoms, such as
ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and
aromatic aliphatic diols, such as the bis-(2-hydroxyethyl)
ether of hydroquinone.
Another feature of the process according to this
invention is the use of water, which reacts with the iso-
cyanate mixture and provides carbon dioxide as the blowing
- 8 -
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~L~L2~599
agent. Preferably used are 2 to 6 percent by weight, in
particular 2.5 to 3.5 percent by weight, of water, relative to
the weight of the polyol. Instead of water alone, mixtures of
water and chemically inert, low-boiling, possibly halogenated
hydrocarbons or e-thers can be us~d as blowing a~ents.
Examples of substances which may possibly be used are
optionally halogenated hydrocarbons having boiling points
below 50C, preferably between -50 and 30C, under atmo-
spheric pressure. To be mentioned in detail are halogenated
hydrocarbons, such as monochlorodifluoromethane, dichloro-
monofluoromethane, dichlorodifluoromethane and trichloro-
fluoromethane and their mixtures, and hydrocarbons, such as
propane and isobutane, as well as dimethyl ether.
Suitable mixtures of water and possibly halogenated
hydrocarbons generally consist of 5 to 70 percent by weight,
preferably 10 to 50 percent be weight, of water/ and 30 to 95
percent by weight, preferably 50 to 90 percent by weight, of
possibly halogenated hydrocarbons, with the percentages by
weight being based on the total weight of the blowing agent
mixture. The required quantities of blowing-agent mixtures
can be determined by simple experimentation as a function of
the mixing ratio of water to possibly halogenated blowing
agents as well as of the desired foam density, and are ap-
proximately 2 to 40, preferably 5 to 25, percent by weight,
based on the polyol weight.
Catalysts which accelerate the polyurethane
formation and, optionally, auxiliaries and additives which are
commonly used for :the manufacture of flexible polyurethane
foam, can also be added to the foamable reaction mixture.
These include, for instance, surface-active materials, flame
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~29S99
inhibitors, pore regulators, antioxidants, hydrolysis-
protection agents, dyes, fillers and other additives.
Sultable catalysts for accelerating the reaction
between the polyols, the water, and optional chain-extension
agents, on the one hand and the urethane-modlfied poly-
isocyanate mixture according to this invention, ~n the other
I hand, include tertiary amines such as dimethylbenzylamine,
; N,N~N',N'-tetramethyldiaminodiethyl ether, bis-(dimethyl-
aminopropyl)-urea, N-methyl- or N-ethylmorpholine, dimethyl-
piperazine, 1,2-dimethylimidazole, 1-aza-bicyclo-(3,3,0)-
octane, and preferably! triethylenediamine; metal salts such
- n : . ~
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~29S99
as lead octoate, tin di~2-ethylhexanoate, and preferably,
tin-tII) salts, and dibutyltin dilaurate, as well as,
partlcularly, mixtures of tertiary amines and organic tin
salts.
Preferably used are 0.5 tQ 5 percent by weight
catalyst based on tertiary amines and/or 0.01 to 2.5 percent
i by weight of metal salts, based on the polyol weight.
Other possible materials to be used include surface-
active substances which support the homogeni2ation of the-raw
materials and which are also possibly suited to regulate the
I cell structure of the flexible polyurethane foams. To be
! mentioned as examples are siloxane-oxyalkylene,mixed pdly~ers
and other organic polysiloxanes, oxyethylated aIkylphenol,
¦ oxyethylate fatty alcohols, paraffin oilsj castor oil or ~ .
! ricinoleic ester, and turkey red oil, whlch are used in
'
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~L29599
quantities of 0.2 to 6 parts by weight per 100 parts by weight
of the urethane-modified polyisocyanate mixture.
In order to improve the flame resistance, flame
inhibitors may be added to the flexible polyurethane foams
manufactured in accordance with this invention. To be
mentioned as examples are compounds containing phosphorus
and/or halogen atoms which furthermore can reduce the tendency
toward brittleness of the products and function as plasticizers.
These include tricresyl phosphate, tris-2-chloroethyl phosphate,
tris-chloropropyl phosphate, and tris-2,3-dibromopropyl
phosphate; inorganic flame inhibitors such as antlmony
trioxide, arsenic oxide, ammonium phosphate, amm0nium sulfate,
and others; and preferably, cyanic acid derivatives such as
cyanamide, dicyandiamide, guanidine, and in particular,
guanidine salts, biguanidine, and particularly, melamine.
Cyanic acid derivatives of the referenced type are described,
for instance in copending Canadian Patent Applicatio~ Serial
No. 325,402 filed April 10, 1979. It has generally proven
to be advantageous to use 5 to 70 parts by weight, preferably
10 to 50 parts by weight, of the above-referenced flame
inhibitors per 100 parts by weight of the urethane-modified
polyisocyan'ate mixture.
More detailed data concerning the above-mentioned
other commonly used auxillaries and additives are described
in the literature, such as the monograph by J.H. Saunders and
K.C. Frisch, " High Polymers" volume XVI, Polyurethanes,
Parts 1 and 2, Interscience Publishers, 1962 and 1964.
. . . . . . . . .. . .. . . . ... . . _ _ _ . _ _ . .. ... ... . . .
~Z~S~9
The flexible polyurethane foams may be produced
according to the prepolymer process and preferably, according
to the one-shot process.
If the flexi~le polyurethane foams are produced
according to the one-shot proces~s, a mixture of polyol, water,
catalyst, and possibly chain extenders, auxiliaries and
additives, is usually brought to reaction with the urethane-
modified polyisocyanate mixture to be used according to this
invention at temperatures of 15 to 60C, preferably 25 to
40C, in such quantities that the ratio of hydro~yl groups of
the polyols and optional, chain extenders to the NC0 groups of
the urethane-modified polyisocyanates is 0.1:1 to 0.4:1,
preferably 0.15:1 to 0.3:1, and that the ratio of all
Zerewitinoff active-hydrogen atoms -- bonded to polyol,
optional chain extenders, and water -- to the NCO group of the
urethane-modified polyisocyanate mixture is approximately 0.7
to 1.3:1, preferably 0.9 to 1.1:1. When usin~ a mixin~
chamber with several feed nozzles, the liquid raw material can
be introduced individually, or if the components are solid, in
form of solutions or suspensions, and can be mixed intensively ~
in the mixing chamber. However, it has proven to be particu- ::
larly appropriate to work according to the two-component :
method and to combine the mixture of polyol, water, catalyst,
optional chain extenders, auxiliaries and additives, as
component A and to use the polyisocyanate mixture as component
B.
In order to manufacture the NC0-group-containing
prepolymers for the prepolymer polyurethane process, the
urethane-modified polyisocvanate mixture to be used in ac- `~
cordance with the invention is reacted with the above-
mentioned polyols and/or chain extenders in such quanti-
ties that the ratio of NCO groups to total hydro~yl is 1.8:1
- 13 -
~2gs99
to 55:1, preferably 4:1 to 45:1. The resulting pxepolymers
are subsequently mixed with water or mixtures consisting of
water and low-boiling, possibly halogenated hydrocarbons and
possibly additional polyols and/or chain extenders and
auxiliaries and additives, and are allowed to foam.
The flexible polyurethane foams are initiated at
elevated temperatures, such as temperatures between 15 and
60C, preferably between 35 to 45C. A.post-heating process
is generally not required.
The flexible polyurethane foams produced in ac-
cordance with this invention have densities of approximately
20 to 150 grams per liter and excel particularly because of
theirvhigh load-bearing capacity, tear strength, and tensile
strength.
The products are particularly well suited for the
manufacture of upholstered furniture, automobile seats, head
supports, molded pieces, and foam backing of foils.
The parts referred to in the examples are parts by .
weight.
Example 1 - ::
Manufacture of Urethane-Modified Poly _ocyanate Mixtures
To 95 parts of a mixture of diphenylmethane dl- .
isocyanates and polyphenylene polymethylene polyisocyanates : :
containing approximately 65 percent by weight of diphenyl-
methane diisocyanate, and approximately 10 percent by weight :
of three functional isocyanates, 5 parts of oligomeric
propylene glyco:Ls with an average molecular weight of 250 are
added at room temperature and, while the mixture is agitated,
the mixture is heated at 80C for 2 hours and is subsequently
cooled. A urethane-modified polyisocyanate mixture with an
NCO content of 28.6 percent by weight and a viscosity of 140
centipoises at 23C is obtained.
- 14
~i29S99
Proceeding ln accordance with the method glven in
Example 1, but using the raw materials and quantities sum-
marized in Table I, the urethane-modified polyisocyanate
mixtures listed in that`table are obtained.
The following abbreviations were used in Table I:
Crude MDI: Mixture of diphenylmethane diisocyanates and
polyphenylene polymethylene polyisocyanates
Pure MDI: 4,4'-diphenylmethane diisocyanate 99.9 percent
purity
10 Mixture: Mixture obtained irom crude MDI and pure MDI
C6-diol: Mixture.of isomeric diols with 6 carbon atoms
having an average molecular weight~of approx'i-_
mately 118
PP-10: Polypropylene glycol having an average molecular.
weight of 1000
PP-4: Polypropylene glycol having an average molecular
weight of 400
.. . . . . _ . _
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~2~599
Manufacture of Polyurethane Foams
Component A: .
For Examples 2 to 3 and Comparison.Examples I to V,
the same mixture was used as Component A. The mixture con-
sisted of:
100 parts of a polyether polyol based on dipropylene
glycol-propylene oxide-ethylene oxide with an OH
number of 29,
3.2 parts of water,
0.1 part of amine catalyst (commercial product Desmorapi
PV by Bayer AG, Leverkusen?,
0.17 part bis(beta-(N,~-dimethylaminoethyl)-ether,
0.17 part of triethylenediamine, and
1.4 parts of a foam stabilizer based on polysiloxane-poly-
oxyalkylene (commercial product Tegostab~ B 4690 by
Goldschmitt AG, Essen).
Example 6
To 105 parts of Component A are intensively mixed
61.3 parts of the polyisocyanate mixture according to Example
1 at 25C. Subsequently, the mixture is allowed to foam.
The foamable polyurethane mixture displays normal
foaming behavior (cream time 15 seconds; rise time 85 seconds).
The mechanical properties of the resulting foam have been
summarized in Table II.
Example 7
To 105 parts of Component A are intensively mixed
69.8 parts of the polyisocyanate mixture in accordance with .
Example 2 at 35C and are subsequently aliowed to foam at a
mold temperature of 55C.
The cream time is 12 seconds; the rise time is 70
seconds. The mechanical properties of the well processable
foams are summarized in Table II.
- 17 -
' . . .:. .
.
`` ~lZ9599
,.
Exa~ple 8
A mixture of
630 parts of a polyether polyol based on dipropylene
glycol, propylene oxide, ethylene oxide with an OH
number of 29,
parts of a polyester polyol based on adipic acid,
ethylene glycol and 1,4-butanediol with an OH number
of 56,
16.8 parts of water,
parts of trichlorofluoromethane,
2.8 parts amine catalyst (commercial product Desmorapid~
- PV by Bayer AG, Leverkusen),
1.4 parts of triethylenediamine, and
parts of a fo.am stabilizer based on polysiloxane-poly-
oxyalkylene (Tegostab B 4690) is mixed intensively
with
375 parts of the polyisocyanate mixture in accordance with
Example 1 at 30C and is allowed:to foam. The -mechanical properties of the resulting foams are
summarized in Table II.
Example 9 :~ .
A mixture of
300 parts of a polyether polyol based on dipropylene
glycol, propylene oxide, ethylene oxide with an OH
number of 29,
11.7 parts of water, ;.
105 parts of dimethylethanolamine, . ~:
1.05 parts of triethylenediamine,
1.2 parts of tin dioctoate,
302.1 parts of a foam stabilizer based on polysiloxane-poly-
oxyalkylene (Tegostab BF 2370 by Goldschmitt AG,
Essen~, and
,',
- 18 -
1~29S99
parts of trichlorofluoromethane is mixed intensively
with 230 parts of the polyisocyanate mixture in
accordance with Example 1 at temperatures of 30C and
is subsequently allowed to foam.
The mechanical properties of the resultiny foams are
summarized in Table II.
Comparison Example I
To 105 parts of Component A are intensively mixed
56.6 parts of a commercially available mixture consisting of
diphenylmethane diisocyanates and polyphenylene polymethylene
polyisocyanates (Crude MDI) having a viscosity of 200 centi-
poises and containing approximately 40 percent by weight of
diphenylmethane diisocyanate and a three functional isocyanate
content of approximately 20 percent by weight and the mixture
is subsequently allowed to foam at 25C.
The cream time in this case is 15 seconds; the
tack-free time is 120 seconds. The resulting polyurethane
foam has poor gas yield and poor tear strength. The :. ~ -
mechanical properties are listed in Table II.
Com~arison Example II
To 105 parts of Component A are intensively mixed ~ :
55.5 parts of a mixture of 77.8 parts of crude MDI containing
approximately 40 percent by weight of diphenylmethane di- -
isocyanate and 22.2 parts of 4,4'-diphenylmethane diisocyanate
(the mixture has an average diphenylmethane diisocyanate
content of approximately 54 percent by weight and a three :
functional isocyanate content of approximately 17 percent by :,
weight) and is allowed to foam at 25C.
The determined cream and rise times were 12 and 80 . :
seconds.
The polyurethane foams had a modest gas yield and
unsatisfactory mechanical properties (see Table II).
-- 19 --
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_omparison Example III
T 105 parts of Component A are mixed intensively
54.5 par-ts oE a mixture of 55 parts crude MDI and 4~.5 parts
4,4'-diphenylmethane diisocyanate (the mixture has an average
diphenylmethane diisocyanate content oE approximately 67
percent by weight and a -three func-tional isocyanate content of
11 to 14 percent by weight) and the mixture is allowed to foam
at 25C.
The initially formed foam collapses completely.
Comparison Example IV
To 105 parts of Component A are mixed intensively
53.6 parts of a mixture consisting of 33.4 parts of crude MDI
and 66.6 parts of 4,4'-diphenylmethane diisocyanate (the ~ ;
mixture has an average diphenylmethane diisocyanate content of
80 to 81.5 percent by weight and a three functional isocyanate
content of 7 to 8.5 percent by weight) and the mixture is
allowed to foam at 25C.
The foam collapses completely.
Comparison Example V
To 105 parts of Component A are mixed intensively
a mixture consisting of 10 parts of crude MDI and 90 parts of
4,4'-diphenylmethane diisocyanate which was midified with 10
parts of neopen-tyl glycol (the urethane-modified polyiso- ~`
cyanate mixture had a diphenylmethane diisocyanate content of
95 percent by weight) and the mixture is allowed to foam at ~ ~;
25C.
The foam collapses.
Comparison Example VI
According to teachings of British Patent 874,430, a
mixture of
97.7 parts of a polypropylene glycol having a molecular
weight of approximately 2000,
~ 21 -
~zgs99
0.7 parts of dimethylcyclohexylamine,
l part ethoxylated octylphenol, and
2 parts water
is mixed intensively with 42~3 parts of a mixture
consisting of 25 parts of crude MDI and 75 parts of
4,4'-diphenylmethane diisocyanate (the average two
functional isocyanate content of the mixture is 85
percent by weightj and the mixture is allowed to foam
at 25C.
The foam collapsed completely and a non-useable
powdery mass was obtained.
In contrast to this, foams with good mechanical
- properties can be produced with the urethane-modified poly-
isocyanate mixtures according to Examples l through 5.
Example 10
Polyol Component B:
For Example 10 and Comparison Example VII, the same ~ ;
mixture was used as polyol Component B. This mixture consisted
of:
20 900 parts of a polyether diol based on dipropylene glycol,
propylene oxide and ethylene oxide having predominantly
primary hydroxyl groups and an OH number of 28,
27 parts of water,
2 parts of Desmorapid PV,
2 parts bis-~beta-(N,N-dimethylaminoethyl~7 ether,
2 parts of triethylenediamine,
parts of Tegostab B 4690, and
l part of dibutyltin dilaurate.
To 200 Parts of polyol Component B are intensively
mixed 127.3 parts of a prepolymer having an NCO content
of 23.7 percent by weight and a viscosity of 680 centipoises
at 23C. The prepolymer has the following composition:
.~
.
- 22 -
~ IL29S99
43.2 parts of 4,4'-diphenylmethane diisocyanate,
31.8 parts of crude rlDI (the resulting mixture has a two
functional isocyanate content of approximately 75
percent),
3 parts of a polypropylene glycol having an average
molecular weight of approximately 400,
2 parts of neopentyl glycol, and
parts of a polyether diol based on dipropylene glycol,
propylene oxide and ethylene oxide with predominantly
primary hydroxyl groups and an OH number of 28.
The mixture is subsequently allowed to foam. The resulting
foam displays good mechanical properties.
Comparison Example VII
To 200 parts of the polyol Component B are inten-
sively mixed 111.3 parts of a prepolymer having an NCO
content of 27.15 percent by weight and a viscosity of 170
centipoises at 23C. The prepolymer was prepared from the
following composition:
43.2 parts 4,4'-diphenylmethane diisocyanate,
31.8 parts crude MDI, and
parts of a polyether diol based on dipropylene glycol,
propylene oxide and ethylene oxide with predominantly
primary OH groups and an OH number of 28.
The mixture is subsequently allowed to foam. The foam totally
collapses.
' '
~ -23 -
.. . . . . . , .. .. ~ . .. .. .. . .
